WO1999023118A1 - Reaction d'un polyhydroxypolymere ou d'un derive de celui-ci avec une lactone - Google Patents

Reaction d'un polyhydroxypolymere ou d'un derive de celui-ci avec une lactone Download PDF

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Publication number
WO1999023118A1
WO1999023118A1 PCT/IB1998/001734 IB9801734W WO9923118A1 WO 1999023118 A1 WO1999023118 A1 WO 1999023118A1 IB 9801734 W IB9801734 W IB 9801734W WO 9923118 A1 WO9923118 A1 WO 9923118A1
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WO
WIPO (PCT)
Prior art keywords
derivative
cellulose
polymer
reaction
polyhydroxy
Prior art date
Application number
PCT/IB1998/001734
Other languages
German (de)
English (en)
Inventor
Jürgen LOERCKS
Claudio Pellegrini
Harald Schmidt
Ivan Tomka
Original Assignee
Bio-Tec Biologische Naturverpackungen Gmbh & Co.Kg
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bio-Tec Biologische Naturverpackungen Gmbh & Co.Kg filed Critical Bio-Tec Biologische Naturverpackungen Gmbh & Co.Kg
Priority to JP2000518988A priority Critical patent/JP2001521947A/ja
Priority to AU95546/98A priority patent/AU9554698A/en
Priority to EP98949178A priority patent/EP1028981A1/fr
Publication of WO1999023118A1 publication Critical patent/WO1999023118A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/06—Cellulose acetate, e.g. mono-acetate, di-acetate or tri-acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/02—Esters
    • C08B31/04—Esters of organic acids, e.g. alkenyl-succinated starch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification
    • C08F8/16—Lactonisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule

Definitions

  • the present invention relates to a process for reacting at least one polyhydroxy polymer and / or a polyhydroxy polymer derivative with at least one lactone, a lactam or a suitable carboxylic acid and a thermoplastic biodegradable composition based on polyhydroxy polymer derivatives, comprising a reaction product of at least one a polyhydroxy polymer and / or a polyhydroxy polymer derivative and at least one lactone, a lactam or a suitable carboxylic acid.
  • Polymers and polymer mixtures based on polyhydroxy polymers such as in particular polyhydroxyacetal, polyvinyl alcohol, polyvinyl alcohol-polyvinyl acetate copolymer, polyvinyl alcohol acetal or a polyhydroxy ether, or based on a polyhydroxy polymer derivative by reaction with alcohols, fatty acids, esters, such as, in particular, lactones , in solutions or suspensions with useful properties, are known.
  • thermoplastic compositions consisting of mixtures of cellulose esters and / or ethers which are mixed with cyclic esters.
  • ⁇ -caprolactone is used as the cyclic ester, the mechanical properties of the polymer mixtures produced being inadequate.
  • GB 2 152 944 and the two Japanese patent applications JP 59-86621 and JP 60-188402 describe the reaction of cellulose acetate with cyclic esters such as caprolactone, the reaction mixture in xylene being used as a solution or Plasticizer is dissolved.
  • plasticizers such as diethyl phthalate or dimethyl phthalate are additionally added to the reaction mixture.
  • EP 0 635 649 proposes adding a plasticizer to the cellulose acetate first. This is intended to reduce the amount of lactone required, which is associated with a reduction in costs.
  • These additional plasticizers are alcohol derivatives. Depending on the mixing ratio of this alcohol derivative and the lactone, the properties of the plasticized cellulose acetate can be adjusted.
  • plasticization of cellulose derivatives or generally polyhydroxy polymers such as in particular polyhydroxyacetal, polyvinyl alcohol, polyvinyl alcohol-polyvinyl acetate copolymers, polyvinyl alcohol acetal or polyhydroxy ether or derivatives thereof, by adding plasticizers, as well as that Use of solvents and the like is undesirable because these plasticizers, solvents and the like remain in the polymer to be produced.
  • plasticizers, solvents and the like remain in the polymer to be produced.
  • onomeric portions or traces of solvent which have not been removed are inadmissible in food foils, since these low molecular weight fractions can slowly diffuse out of the foil, which jeopardizes their suitability for foodstuffs.
  • a method for producing such a polymer based on polyhydroxy polymer or polyhydroxy polymer derivative according to the wording according to claim 1 or 2 is proposed, and a corresponding polymer based on polyhydroxy polymer derivatives according to the wording according to claim 21.
  • the polyhydroxy polymer according to the present invention is a polyhydroxyacetal such as polysaccharide, polyvinyl alcohol, such as a polyvinyl alcohol-polyvinyl acetate copolymer, polyvinyl alcohol-polyethylene-
  • Copolymer to polyvinyl alcohol acetal or a polyhydroxy ether such as polyglycerol, polyerithritol, polypentaerithritol, polysorbitol, polymannitol, polyethylene glycol, polypropylene glycol, poly 1, 3-propanediol, etc.
  • the reaction between the polyhydroxy polymer or the polyhydroxy polymer derivative and the lactone and / or optionally the further reaction partner, such as a lactam or a selected carboxylic acid, such as, for example, formic acid takes place continuously in the homogeneous phase, for example in an extruder or kneader in which, on the one hand, owing to the thorough mixing, the diffusion paths between the reactants are very short, in contrast to, for example, batch or pot reactions.
  • relatively short residence times or reaction times are chosen, with which the chain length of the polymer remains practically unchanged, ie there is no degradation of the polyhydroxy polymer derivative.
  • an extruder or kneader when mixing and reacting the polyhydroxy polymers with a lactone, a lactam or a selected carboxylic acid, since this enables the reaction partners to be mixed as homogeneously as possible.
  • Polyhydroxy polymers are rather hydrophilic, while, for example, lactones are rather hydrophobic, which means that the mixture is then two-phase, unless high shear conditions of an extruder or kneader are used.
  • the high shear conditions result from the geometry of the bore and the screw or screws in the extruder or kneader as well as from the high pressure that is built up along the screw in the extruder.
  • the advantage of the present invention is in particular that the quasi-solvent or the plasticizer in the homogeneous phase are simultaneously the reactants to the polyhydroxy polymer or the derivative thereof and are largely, preferably completely, incorporated into the polyhydroxy polymer during the reaction.
  • further workup of the polyhydroxy polymer derivative produced according to the invention is therefore unnecessary. Any water arising as a result of the esterification reaction or any residual water within the polyhydroxy polymer can be removed in the extruder along the screw or, if appropriate, before the material is ejected by venting, in particular in order to shift the balance of the esterification reaction to a higher degree of esterification.
  • the reaction product can be processed thermoplastically without the need to add other plasticizers.
  • Other benefits include the following:
  • the mechanical properties for example of foils, films, fibers, produced according to the described extrusion processes show useful or good mechanical properties, such as:
  • polyhydroxy polymers such as polysaccharides or polyvinyl alcohols, such as, in particular, inexpensive, partially hydrolyzed polyvinyl acetates which are water-soluble.
  • Polyvinyl alcohol-polyethylene copolymers for example, are too hygroscopic and lose water barrier properties if used as film materials. This can be counteracted by reacting such partially hydrolyzed polyvinyl alcohol or the polyvinyl alcohol-polyethylene copolymer mentioned with caprolactone.
  • polyvinyl alcohol acetals Polyglycerin is inexpensive but too hy wholesale copy. This can be counteracted by reaction with caprolactone.
  • Arabicum Acacia gum, tragacanth, carragenan, furcelaran, ghatti, guar, locust bean, psyllium, quince, tamarind-karaya gum;
  • Fermentation products dextran, xanthan, curdlan, scleroglucan;
  • Bacterial extracts yeast glucan, pullulan, Zanflo-10, Zanflo-21: Reg.Mark Kelco Division, Merck & Co., Inc., PS-7: Azotobacter indicus, Bacterium alginate: Azotobacter vinelandii,
  • Celluloses and cellulose derivatives such as carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, as well as further methyl ether of pectin, hydroxypropyl alginates;
  • Shellfish extracts, chitin and chitosan Shellfish extracts, chitin and chitosan.
  • Formates acetates, butyrates, propionates or generally esters, ethers, alkyl ethers such as, for example, ethyl cellulose, methyl cellulose etc. and carboxymethyl derivatives such as hydroxyalkyl ethers, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose. It is essential that the derivative or derivatives are soluble in lactones.
  • Corn starch potato starch, corn sugar, agar, Arabic gum, guar, pectin, carboxymethyl cellulose and xanthan, to name just a few examples.
  • Polysaccharide acetate (diacetate), formate, butyrate and propionate, such as cellulose sulfate (diacetate), formate and butyrate, have proven to be particularly suitable polysaccharide derivatives, the degree of substitution being at least about 1.5, however should not be higher than approx. 2.6.
  • Caprolactone, dilactide and diglicidyl lactone (2-glycolic acid) and corresponding lactams, such as, for example, caprolactam or carboxylic acids, such as, in particular, formic acid, are particularly suitable as lactones or other reaction partners.
  • the polysaccharide again representative of a polyhydroxy polymer, or the derivative thereof, for example 1, 3 Polyglucan, cellulose formate, chitin formate or starch formate is preferably first premixed with the lactone, such as caprolactone, at room temperature and then introduced into an extruder or kneader, where the two reaction partners are melted.
  • the lactone such as caprolactone
  • the reaction takes place between the polysaccharide derivative and the lactone, it being possible for any monomers present in the reaction mixture, such as, in particular, unreacted lactone as well as low-molecular reaction products formed and excess water to be removed by degassing.
  • the polymer or reaction product finally produced preferably contains as little or no monomers as possible which can diffuse out of the polymer.
  • alkoxylates of alkali and alkaline earth metals, as well as rare earths have proven to be catalysts for carrying out the proposed reaction.
  • alkoxylates of Group IV metals are also suitable, such as, in particular, titanium alkoxylates, which titanium compounds are known from the prior art, for example GB 2 152 944 and EP 636 649.
  • reaction product preferably contains essentially only highly polymeric substances, i.e. no small molecules that can diffuse out. This is due to the requirement, for example, for food suitability, as well as the requirement for good mechanical properties;
  • reaction is carried out in an extruder, which makes it possible to at least largely be able to remove all low molecular weight substances.
  • care must be taken to ensure that the alcohols released can be removed by degassing.
  • the chain length should preferably not change. In other words, care must be taken when carrying out the reaction that the polyhydroxy polymer derivative is not degraded. Again, this can be achieved by choosing the extrusion reaction, for example, since, as mentioned above, there are very short diffusion paths between the reaction partners in the extruder. This is in contrast to batch reactors or so-called "pot reactors". In the case of a batch reaction, the reaction time is usually too long, so there is a risk of the basic structure of the polyhydroxy polymer or the polyhydroxy polymer derivative being degraded.
  • the preferably biodegradable polymers proposed according to the invention can also be obtained by mixing the polyhydroxy polymer or polyhydroxy polymer derivative (s) with at least one other biodegradable polymer or polyhydroxy polymer or derivatives thereof before or during reaction with the lactones, lactams or suitable carboxylic acids (for example) starch, a starch derivative such as starch acetate, chitin and / or cellulose.
  • thermoplastically processable starch is a starch which is produced from native starch using a suitable plasticizer or swelling agent, and when reacting in the melt of the native starch with the plasticizer or swelling agent, the moisture is released is reduced to less than 5% by weight, preferably to less than 1% by weight.
  • Suitable plasticizers or swelling agents are, in particular, glycerol, sorbitol or preferably, in turn, the lactones or lactams mentioned at the outset, such as, in particular, ⁇ -caprolactone, ⁇ -caprolactam and polymers produced therefrom, such as, for example, polycaprolactone.
  • the softening point (EP) of materials is an important criterion for defining the range of use under practical and environmental conditions.
  • the softening points of the common polymers (LDPE, HDPE) of a biodegradable polymer, ie of polycaprolactone were examined and compared with the softening points of the cellulose acetate derivatives from Table 2, experiments 15 and 16. The corresponding measured values are shown in Table 4 below: Table 4: Heat resistance of PCL, LDPE, HDPE and CA derivatives:
  • a polymer to be suitable as a packaging material it must have good heat resistance.
  • the minimum requirement is that the heat resistance is> 100 ° C, i.e. according to the value for LDPE.
  • the plasticized cellulose acetate produced for example in accordance with EP 636 649 have a heat resistance which is below 100 ° C., which is due to the use of the plasticizer.
  • Table 4 it can be seen from Table 4 that, for example, pure PCL is not a suitable material due to its poor heat resistance.
  • SA degree of substitution
  • DS degree of substitution
  • the starting compounds i.e. Derivatives of the three materials listed above, such as cellulose formate, chitin formate and starch formate, were prepared according to a slightly modified regulation by Heinze et al. (Liebert T., Klemm D., Heinze T., J. Mat. Sei. Pure Appl. Chem., A33 (5), 1996, 613-626).
  • Cellulose formate 1.0 g of dry cellulose was mixed with 30 ml of formic acid at room temperature. 2.7 ml of phosphorus oxychloride were added dropwise. After 6 h, the viscous solution was poured onto 200 ml of diethyl ether. The precipitate was filtered and washed well three times with 100 ml of acetone each time. Excess water and formic acid were drawn off under reduced pressure in the extruder.
  • Chitin formate analogous to the production of cellulose formate.
  • Starch formate 1.0 g of dry potato starch was dissolved in 30 ml of formic acid at room temperature. Thereafter, 10 ml of acetic anhydride were added and stirring was continued for two days. The solution was poured onto 200 ml of diethyl ether. The precipitate was washed three times with 100 ml of cold acetone.
  • Cellulose formate (dosing rate 2 kg / h) was dosed as a powder in the water-cooled feeder.
  • a mixture of CL and TEAT (2 parts: 0.035 parts) was injected at a rate of 1.5 kg / h.
  • a vacuum of 300 mbar was applied in zone 6.
  • the emerging strand was air-cooled and granulated.
  • the premix which was prepared in experiment 30, was extruded again at a metering rate of 2 kg / h.
  • the time in the extruder is approx. 5 min.
  • chitin formate or starch formate was used.
  • the caprolactone and catalyst content were changed in further experiments.
  • the reaction temperature was changed in further experiments.
  • the number of passes was increased in further tests.
  • Reaction procedure A premix of 20 g of cellulose acetate with a degree of substitution of 2.45 and 20 g of caprolactone are mixed in a chamber kneader at 160 ° C. and 30 rpm. melted for 15 minutes. Then 50 mg of catalyst are added to 5 g portions of this premix, followed by further treatment at 220 ° C. and 100 rpm. in a twin-screw reflux extruder for 5 to 30 minutes.
  • Titanium tetra butylate Ti
  • Table 7 summarizes both sales and selected mechanical properties.
  • twin-screw extruders used for the reaction extrusion are synchronous twin-screw extruders with tightly intermeshing screw profiles and have individually temperature-controlled kneading zones (for example the Werner & Pfleiderer ZSK type).
  • twin-screw extruders with eight chambers or zones are used, which can optionally be expanded to 10 to 12 zones and have the following structure:
  • Screw speed 230 rpm.
  • Feed zone 1 Compression with degassing of premixed raw materials up to zone 3, gradually melt the mixture
  • Zones 5 - 7 reaction chambers, transition homogenization of the melt, compression, drag and pressure flow, reaction zone pressure build-up, discharge zone 8 evaporation of further volatile
  • biodegradable polymers and lactones, lactams or suitable carboxylic acids generally form clear-sighted to ocher-colored films and foils. They are free of plasticizers and in accordance with the regulations for packaging food in accordance with LMBG (Food and Consumer Goods Act). As a rule, they are completely biodegradable and compostable according to DIN 54900.
  • the processing properties can be varied by varying the melt flow index from (MFI g / 10 ') 5 - 12 for the production of blown films, flat films, (MFI g / 10') 2 - 9 for the production of plates, injection molded products and blow molding of bottles, (MFI g / 10 ') 20 - 30 can be changed and adapted for the production of fibers (at 190 ° C and 2.15 kg load).
  • bags and sacks for collecting compostable waste, garden articles such as plant pots, candle covers, fibers, nonwovens, diaper film, films for letter windows, agricultural films, pyrotechnic products, toys.
  • the new polymer based on polysaccharide derivative is suitable as a blend component for the production of biodegradable materials, as a phase mediator in blends made of hydrophilic and hydrophobic thermoplastics, especially for blends made of destructurized or thermoplastic starch with synthetic degradable polymers.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La réaction d'au moins un polyhydroxypolymère ou d'un dérivé de celui-ci avec au moins une lactone, un lactame ou bien un acide carboxylique approprié, en vue de la fabrication d'un polymère de préférence biodégradable, s'effectue dans un bain de fusion homogène, de préférence au moyen d'une réaction d'extrusion.
PCT/IB1998/001734 1997-11-05 1998-10-30 Reaction d'un polyhydroxypolymere ou d'un derive de celui-ci avec une lactone WO1999023118A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2000518988A JP2001521947A (ja) 1997-11-05 1998-10-30 ポリヒドロキシポリマー又はその誘導体とラクトンとの反応
AU95546/98A AU9554698A (en) 1997-11-05 1998-10-30 The reaction of a polyhydroxy polymer or a derivative thereof with a lactone
EP98949178A EP1028981A1 (fr) 1997-11-05 1998-10-30 Reaction d'un polyhydroxypolymere ou d'un derive de celui-ci avec une lactone

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
CH255897 1997-11-05
CH134998 1998-06-24
CH1349/98 1998-07-15
CH2558/97 1998-07-15
CH1514/98 1998-07-15
CH151498 1998-07-15

Publications (1)

Publication Number Publication Date
WO1999023118A1 true WO1999023118A1 (fr) 1999-05-14

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EP (1) EP1028981A1 (fr)
JP (1) JP2001521947A (fr)
CN (1) CN1278268A (fr)
AU (1) AU9554698A (fr)
WO (1) WO1999023118A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2816310A1 (fr) * 2000-11-06 2002-05-10 Universit De Bretagne Sud Procede d'obtention de nouveaux esters d'amidon et leurs applications
WO2009126178A1 (fr) * 2008-04-07 2009-10-15 Biotech Products, Llc Compositions de polymères d'oléfines pouvant être compostées
WO2010121105A1 (fr) * 2009-04-18 2010-10-21 Solutia Inc. Production continue de poly(vinyl butyrale)
US8153783B2 (en) 2001-10-23 2012-04-10 Innogel Ag Polysaccharide based network and method for the production thereof
US8487018B2 (en) 2005-01-24 2013-07-16 Biotech Products, Llc Heavy metal-free and anaerobically compostable vinyl halide compositions, articles and landfill biodegradation
DE102014215482A1 (de) * 2014-08-06 2016-02-11 Kuraray Europe Gmbh Verfahren zur Modifizierung von Polyvinylalkoholen
CN108195869A (zh) * 2018-02-07 2018-06-22 广州天赐高新材料股份有限公司 瓜尔胶羟丙基三甲基氯化铵取代度的检测方法

Families Citing this family (7)

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CA2330318A1 (fr) * 1998-04-27 1999-11-04 Larex, Inc. Derives de l'arabinogalactane et compositions les contenant
WO2007099769A1 (fr) * 2006-02-24 2007-09-07 Daicel Chemical Industries, Ltd. Derive de glycane modifie et objet moule en etant compose
JP5219352B2 (ja) * 2006-02-24 2013-06-26 株式会社ダイセル 変性グルカン誘導体および光学用成形体
TW200745171A (en) * 2006-05-09 2007-12-16 Daicel Chem Hydroxyl acid modified glucan derivative and moldings thereof
EP2890481A4 (fr) * 2013-04-26 2016-05-18 Xyleco Inc Traitement d'acides hydroxy-carboxyliques en polymères
US10669357B2 (en) * 2015-08-27 2020-06-02 Polyone Corporation Polyvinyl butyral-g-polylactide copolymer
CN111303570B (zh) * 2020-02-13 2023-06-16 沈阳工业大学 一种可降解复合增塑剂改性的pva及其制备方法

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Publication number Priority date Publication date Assignee Title
DE3512079A1 (de) * 1984-04-09 1985-10-17 Daicel Chemical Industries, Ltd., Sakai, Osaka Cellulose-pfropfpolymer
JPH06287279A (ja) * 1993-03-31 1994-10-11 Dainippon Ink & Chem Inc ラクタイド系グラフト共重合体の製造方法
DE4428211A1 (de) * 1994-08-09 1996-02-15 Buck Chem Tech Werke Hochmolekulare, thermoplastisch verarbeitbare, biologisch abbaubare chemische Substanz und Verfahren zu deren Herstellung
EP0704470A2 (fr) * 1994-09-30 1996-04-03 Daicel Chemical Industries, Ltd. Alcool polyvinylique modifié par du lactone; procédé pour sa préparation; composition de résine antiélectrostatique permanente; résine à fonctions hydroxyles modifiée par du lactone et procédé pour sa préparation
WO1996020220A1 (fr) * 1994-12-23 1996-07-04 Basf Aktiengesellschaft Amidons thermoplastiques biodegradables
WO1998006755A1 (fr) * 1996-08-09 1998-02-19 Biotec Biologische Naturverpackungen Gmbh Melanges polymeres d'amidon ou de derives de l'amidon pouvant etre faconnes a l'etat thermoplastique

Patent Citations (6)

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Publication number Priority date Publication date Assignee Title
DE3512079A1 (de) * 1984-04-09 1985-10-17 Daicel Chemical Industries, Ltd., Sakai, Osaka Cellulose-pfropfpolymer
JPH06287279A (ja) * 1993-03-31 1994-10-11 Dainippon Ink & Chem Inc ラクタイド系グラフト共重合体の製造方法
DE4428211A1 (de) * 1994-08-09 1996-02-15 Buck Chem Tech Werke Hochmolekulare, thermoplastisch verarbeitbare, biologisch abbaubare chemische Substanz und Verfahren zu deren Herstellung
EP0704470A2 (fr) * 1994-09-30 1996-04-03 Daicel Chemical Industries, Ltd. Alcool polyvinylique modifié par du lactone; procédé pour sa préparation; composition de résine antiélectrostatique permanente; résine à fonctions hydroxyles modifiée par du lactone et procédé pour sa préparation
WO1996020220A1 (fr) * 1994-12-23 1996-07-04 Basf Aktiengesellschaft Amidons thermoplastiques biodegradables
WO1998006755A1 (fr) * 1996-08-09 1998-02-19 Biotec Biologische Naturverpackungen Gmbh Melanges polymeres d'amidon ou de derives de l'amidon pouvant etre faconnes a l'etat thermoplastique

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Title
DATABASE WPI Week 9445, Derwent World Patents Index; AN 363628 *
PATENT ABSTRACTS OF JAPAN vol. 95, no. 1 28 February 1995 (1995-02-28) *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2816310A1 (fr) * 2000-11-06 2002-05-10 Universit De Bretagne Sud Procede d'obtention de nouveaux esters d'amidon et leurs applications
US8153783B2 (en) 2001-10-23 2012-04-10 Innogel Ag Polysaccharide based network and method for the production thereof
US8487018B2 (en) 2005-01-24 2013-07-16 Biotech Products, Llc Heavy metal-free and anaerobically compostable vinyl halide compositions, articles and landfill biodegradation
WO2009126178A1 (fr) * 2008-04-07 2009-10-15 Biotech Products, Llc Compositions de polymères d'oléfines pouvant être compostées
WO2010121105A1 (fr) * 2009-04-18 2010-10-21 Solutia Inc. Production continue de poly(vinyl butyrale)
DE102014215482A1 (de) * 2014-08-06 2016-02-11 Kuraray Europe Gmbh Verfahren zur Modifizierung von Polyvinylalkoholen
CN108195869A (zh) * 2018-02-07 2018-06-22 广州天赐高新材料股份有限公司 瓜尔胶羟丙基三甲基氯化铵取代度的检测方法

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AU9554698A (en) 1999-05-24
EP1028981A1 (fr) 2000-08-23
CN1278268A (zh) 2000-12-27
JP2001521947A (ja) 2001-11-13

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